Combinations of synthetic and natural macromolecules offer a route to new functional materials. While biological and polymer chemistry may not be natural bedfellows, many researchers are focusing their attention on the benefits of combining these fields. Recent advances in living radical polymerization have provided methods to build tailor-made macromolecular moieties using relatively simple processes. This has led to a plethora of block copolymers, end-functional polymers and polymers with a whole range of biological recognition abilities. This review covers work carried out until late 2006 combining living radical polymerization with proteins and peptides in the rapidly-expanding field of bioconjugation. [GRAPHICS] PHICS] in situ reduction, a large number of metal-based functional materials can be prepared. PVP is alkaline, and thus capable of catalyzing the sol-gel process to generate an inorganic shell. Furthermore, pre-formed nanoparticles can also be absorbed by the shell through specific interactions. The PS core is not infiltrative during synthesis, and hollow rings can be derived after the polymer templates are removed. [GRAPHICS] b